1,5-Dinitrenonaphthalene was prepared in two cryogenic matrices by photolysis of 1,5-diazidonaphthalene; the cryogenic matrices were an argon matrix at 11 K and a glassy 2-methyltetrahydrofuran matrix at 77 K; the photolysis was analyzed by UV-VIS, FT-IR, and ESR matrix isolation spectroscopies.